Sulphonated ethers



Patented Apr. 30, 1946 SULPHONATED ETHERS Charles Graenacher and Just Frel, Biehen, and

Jules Meyer, Basel, Switzerland, assignors to the Swiss firm of Society of Chemical Industry in Basic, Basel, Switzerland No Drawing. Application February 5, 1943, Serial No. 474,898. In Switzerland January 9, 1942 6 Claims.

It has been found that new sulphonated ethers containing at least one aralkyl radical are obtained if sulphonated hydroxy compounds are etheriiied by treatment with aralkylating agents containings at least 8 carbon atoms, or if hydroxy compounds are etherifled by treatment with analirylating agents containing at least 8 carbon atoms and the ethers obtained are thereupon sulphonated.

Among sulphonated hydroxy compounds both hydroxy-sulphonic acids as well as sulphuric acidesters of polyhydroxy compounds which contain 1 at least one free hydroxy group are to be understood.

As hydroxy sulphonic acids, use may be made, for example, of those of the aliphatic series, such as hydroxyethane sulphonic acid, chloro-hydroxypropane sulphonic acids, dihydroxypropane sulphonic acids, but preferably, however, of aromatic hydroxysulphonic acids, for instance hydroxy sulphonic acids containing at most two condensed benzene nuclei, that is to say hydroxy sulphonic acids of the benzene and naphthalene series such as mono-hydroxy and dihydroxy naphthalene sulphonic acids. Among these mention may be made of phenol-para-sulphonic acid, chlorophenol sulphonic acids, cresol' sulphonic acids, thymol sulphonic acids, such as 3-hydroxy- 1-methyl-4-isopropylbenzene sulphonic acid-(6) sulphonic acids of resorcinol, such as 1:3-dihydroxybenzene sulphonic acid- (4) sulphonic acids of monoand polyhydroxynaphthalenes, such s l-hydroxynaphthalene sulphonic acid- (4) i-hydroxy-naphthalene sulphonic acid- (5), 2-hydroxynaphthalene sulphonic acid-(6) 2-hydroxynaphthalene disulphonic acid-(3:6), 1:3-dihydreary-naphthalene sulphonic acid-(5) 1:3-dihydreary-naphthalene sulphonlc acid- (6) 2:8-dihydroxynapthalene sulphonic acid- (6), 2:3-dihydroxy-naphthalene sulphonic acid-(6) 1:8-dihydroxynaphthalene sulphonic acid-(4), 1:8-dihydroxycyclohexane sulphonic acids also come into consideration.

Among the sulphuric acid estersof polyhydroxy compounds which also come into consideration as parent materials, mention ma be made of the monosulphuric acid esters of glycol and glycerine.

Chloromethyl compounds of aromatic or partially hydrogenated aromatic compounds are particularly suitable for use as aralkylating agents containing at least 8 carbon atoms. Examples of such substances are: chloromethyl toluene, chloromethyl xylene, chloromethyl cumene, 2- chloromethyl cymene, i-chloromethyl naphthalene, chloromethyl-tetrahydronaphthalenes, such as ar 2 chloromethyl-tetrahydronaphthalene,

chloromethyl-cyclohexyl benzene (prepared, for example, by treating the addition product of benzene and cyclohexene with formaldehyde, aqueous hydrochloric acid, and hydrogen chloride gas at -70 (1.), chloromethyl compounds of higher condensed aromatic ring systems and 01 their partially hydrogenated derivatives, for example,

chloromethylanthracene, chloromethyl-octahydroanthracene, chloromethyl-octahydrophenan threne.

The 'chloromethyl derivatives of aromatic and partially hydrogenated aromatic hydrocarbons which are not yet described in the literature can be prepared directly by analogous processes, for

examplaby introducing hydrogen chloride gas into a mixture-warmed to about (SO- C.of the hydrocarbon, concentrated formaldehyde solution, and concentrated aqueous hydrochloric acid, if desired together with an addition of zinc chloride.

As arallgylating agents, use may also be made of chloromethyl derivatives of hydroxyaryl compounds, for example, the chloromethyl compound hydroxynaphthalene disulphonic acid-(3:6), 2-

hydroxynaphthalene tetrahydronaphthalene, such as ar-tetrahydroq a-naphtholi-sulphonic acid; furthermore hydroxysulphonic acids of diphenyl, anthracene,;

carboxylic acid-(3) -sul- I phonic acid-(6); also hydroxysulphonic acids of also contain other substituents, for example, ami-' no groups. substituted amino groups (such as acylated amino groups) methoxy groups, etc.

Cycloaliphatic hydroxysulphonlc acids such as place preferably at raised temperature, ii desired of the phenol-like addition product of phenol and dipentene, also chloromethyl compounds of ethers containing aryl radicals, for example, the chloromethyl compound of the ether obtained by condensation of dipentene with p-naphthol. These chloromethyl compounds can be obtained from the hydroxyaryl compounds-sometimes described, sometimes to be had directly by nal processes-and their ethers in the manner already described for the 'chloromethyl derivatives of hydrocar ns.

The rea tion of the sulphonated hydroxy compounds, for example, of the hydroxyaryl sulphonlc acids, with the aralkylating agents takes under addition of acid binding agents, such as sodium hydroxide, sodium carbonate, or calcium assess;

Thanks to their capillary activity, the products of the invention can be used as textile auxiliary products, for example, as wetting, dispersing, washing, softening, levelling, or foaming agents.

5 Products of the invention which have nuclear alkylated benzyl radicals, especially those having two such radicals-which may be introduced by means of ehloromethyl cymene-are excellent wetting agents. These cymyl-methyl derivatives possess a much higher wetting capacity than corpounds-this can take place in the or already described for the, hydroxysulphonic acidsand then sulphonating the others thus obtained by, treatment with sulphonating agents, such as concentrated sulphuric acid, chlorosulphonic acid, sulphuric acid containing sulphur trioxide.

The products of the present invention may m designated as sulphonated ethers containing at least one aralkyl radical with at. least 8 carbon atoms bound to an ether oxygen atom, which products in the form of the alkali metal salts are solid to liquid substances soluble in water to form stable capillary active solutions. Other salts than the above mentioned alkali metal salts including ammonium salts, such as amine salts, for instance alkylolamine salts may also be obtained according to the present invention.

The ether sulphonic acids obtained in the reaction of aromatic hydroxy sulphonic acids are sulphonic acids in which at least one nuclear hydrogen atom is substituted by a radical of the formula OR. wherein R stands ior an aralkyl radical with at least 8 carbon atoms. The reaction with ar-Z-chloromethyl-tetrahydronaphthalene leads to sulphonic acids in which at least one nuclear hydrogen atom is substituted by at least one radical of the formula the radical representing a tetrahydronaphthylmethyl radical. The corresponding reaction with z-chlormethylcymene yields sulphonic acids which are representing a cymyl-methyl radical.

responding products which contain naphthylmethyl or tetrahydronaphthylmethyl radicals instead of cymylmethyl radicals. Products containing tetrahydronaphthylrnethyl radicals are noteworthy for their good washing action.

The products of the present invention can be used alone or in combination with other substances which are commonly used in conjunction with textile auxiliary products, for example, in-

as organic salts.

iii?

The following examples illustrate the invention,

the parts being by weight:

Example 1 parts of a pale yellow residue of the formula are obtained, which is readily pulverizable.

The produce yields a clear solution in water and is not precipitated therefrom by acidifying with mineral acid. Its solutions foam strongly and possess good washing powers.

Instead of the sodium salt of 2:6-hydroxygo naphthalene-sulphonic acid the corresponding ammonium salt or an alkylolamine salt may be used. Moreover,-these salts may be replaced by the sodium salt of the fi-hydroxyethane sulphonic acid or of the acid sulphuric acid ester of ethylene glycol.

Example 2 28 parts of a technical sodium salt of 2-hydrOxynflphthalene-G-sulphonic acid with a calculated content of 22.5 parts of the acid are dissolved in parts of caustic soda of 4 per cent. strength and 17.5 parts of 2-chloromethylcymene are added at '75-80 C. whilst stirring well. After about 1% hours an almost clear solution is obtained which has a neutral reaction. This reaction solution is evaporated to dryness, when 45 ports of a pale yellow, easily pulverized residue are obtained. It has the formula NaO H C CHi The product yields a clear solution in water and is not precipitated thereirom when acidified with mineral acid. The aqueous solution foams strongly and possesses good wetting and washing powers.

Example 3 .parts of z-chloromethylcymene are introduced.

After stirring for 1% hours a sample of the reaction mixture should give a clear solution with water. It is now neutralized exactly and evaporated to dryness.

' The sodium salt of the cymylmethyl ether of lhydroxynaphthalene-S-sulphonic acid which is obtained and which has the formula on, o-cm-Q C CH: OINB is a pale yellow powder, readily soluble in water. Its aqueous solutions possess pronounced washing. foaming and wetting properties.

Example 4 32.5 parts of a technical sodium salt of 2:8-di hydroxynaphthalene-G-sulphonic acid with a calculated content or 24 parts or the acid are dis-' solved in 100 parts of water and are made neutral to Congo Red paper with dilute caustic soda. 26.5 parts of caustic soda of 30 per cent. strensth and 36 parts of ar-2-chioromethyltetrahydro- CH O -OCH

H H NaOiS is readily soluble in hot water and is not precipitated from such a solution by mineral acid. The

as: we:

' aqueous solution foams strongly.

Example 32.5 parts of a technical sodium salt of 2:s-a1-' hydroxynaphthalene-B-sulphonic acid (73.8 per cent. of suiphonic acid) are dissolved in 100 parts of water and the solution is neutralized with calls-- tic soda. 27 parts of a solution of caustic soda 01 30 per cent. strength are then added; the solution is heated to 65-70 C.-and, whilst stirring, 86

parts of 2-chloromethylcymenc are added. After stirring for hours the sodium salt of the dicymylmethyl ether of 2:8 dihydroxynaphthalene-B-sulphonic acid separates as a semisolid mass which becomes solid on cooling and is then filtered oil.

The new product thus obtained of the formula CHs--0 CH -O-CH E NBOIB C CHI 3 C CH:

dissolves in water to yield solutions that foam strongly and are pronouncedly capillary active.

Ewample 6 46 parts of a technical sodium salt of 1:8-dihydroxy-naphthalene-G:(i-disulphonic acid with a calculated acid content of 32 parts are suspended in 100 parts of water and are neutralized to Congo Red paper by addition of dilute caustic soda solution. 0n adding 26.5 parts of caustic soda solution of 30 per cent. strength a brown solution is formed which is stirred with 36 parts 01 l-chloromethyl-naphthalene at 60-455 C. After 1% hours the reaction mixture is neutral to Brilliant Yellow paper and a slimy mass separates out. A sample of the latter gives a clear solution in water. After evaporation and drying of the reaction mixture, parts of an easily pulverized residue of the iormula genre 0-0118 sNa NilOsS are obtained;

, The product gives a clear solution in water and is not precipitated therefrom by acidification with mineral acid. The aqueous solution foams strongly and possesses good washing power.

In a similar manner fi-chlormcthylcymene instead oi l-chlormethylnaphthalene may be condensed with the 1:8;3:6-dihydroxy-naphthalene disulphonic acid.

- Example 7 19.6 parts oi sodium para-phenolsulphonate are dissolved in 50 parts by volume or Eli-sodium hydroxide solution at 40-50 C. 18 parts of ar- '2 chloromethyltctrahydronaphthalene are added are insoluble in water, the reaction solution is evaporated to dryness and the residue is extracted with ether, when the sodium salt oi paratetrahydronaphthyl methyl hydroxy benzene sulphonic acid of the formula.

msoOo-cn Bibi Mi i remains as an almost white powder which dissolves in water to yield a foaming solution and possesses pronounced washing action, especially in the presence of common salt.

Example 8 For the washing of woollen yarn a bath is prepared which contains 0.3 to 0.6 gram of the product obtained in Example 1 per liter of water at at C., the ratio of goods to liquor being 1:20. The material is entered into the bath, turned for hour and then rinsed. After this treatment the wool is excellently clean and can be dyed directly without trouble.

What we claim is:

l. Aromatic sulphonic acids in which at least one nuclear hydrogen atom is substituted by a radical of the formula -OR, wherein It stands for an alkylated benzyl radical, free from sulphonic acid groups, with at least 11 carbon atoms, which products in the form of the alkali metal salts are solid to liquid substances soluble in water to form stable capillary active solutions.

2. Sulphonic acids of the naphthalene series in which at least one nuclear hydrogen atom is substituted by the radical of the formula H C CEs which products in the mm of the man m1 I so ' aceacse salts are solid to liquid substances soluble-in waterto form stable capillary active substances.

4. The suiphonic acid of the formula which product in the form of the sodium salt f5 CH: CH: which products in the form of the alkali metal salts are solid to liquid substances soluble in water to form stable capillary active solutions.

6. The sulphonic acid of the formula 35 v on:

which product in the form of the sodium salt is a solidsubstance soluble in water to form stable capillary active solutions of a good washing power.

CHARLES GRAENACKER. JOST FREI. JULES MEYER. 

